共查询到20条相似文献,搜索用时 140 毫秒
1.
Lei Yang 《Inorganica chimica acta》2005,358(15):4505-4510
An organically templated zinc-substituted gallium phosphite, [H3N(CH2)2NH3]1/2 · [GaZn(HPO3)3(H2O)2] was synthesized under mild hydrothermal conditions in the presence of ethylenediamine (en) as structure-directing agent and characterized by single-crystal X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pbcn with unit cell parameters: a = 18.6146(10) Å, b = 11.0454(6) Å, c = 10.9074(4) Å, V = 2242.62(19) Å3 and Z = 8. This compound has a three-dimensional framework built up from secondary building units (SBU) of Ga(III) (or Zn(II)) and HPO3 pseudopyramid by sharing vertices. The structure displays a two-dimensional channel system running along the [0 0 1] and [0 1 0] direction with 5-, 8- and 10-membered rings. The diprotonated ethylenediamine template molecules are located in the channels. In this structure, some of the Ga(III) sites are occupied by Zn(II) atoms. The compound was also characterized by IR spectroscopy, inductively coupled plasma (ICP), X-ray photoelectron spectra (XPS), differential thermal and thermogravimetric analyses. 相似文献
2.
The crystal structure of the title compound [Fe(bpz)3](ClO4)2 · H2O (bpz=2,2′-bipyrazine) has been determined by a single crystal X-ray diffraction study at 293(2) K. The complex is monoclinic, P21/c, a=17.263(3), b=9.983(2), c=17.921(4) Å, β=107.94(3)°, V=2938.3(10) Å3, Z=4, R=0.073 and Rw=0.118. The structure is made up of tris-chelated [Fe(bpz)3]2+ cations, uncoordinated perchlorate anions and crystallization water molecules. The iron atom exhibits a FeN6 distorted octahedral geometry with average Fe-N bond length and N-Fe-N bidentate angle of 1.962(5) Å and 81.6(2)°. The value of the Fe-N bond distance and that of the room temperature magnetic moment are in agreement with a singlet 1A1 ground state. The structure of 1 is compared to those of other tris-chelated iron(II) complexes with bidentate nitrogen heterocycles. 相似文献
3.
The binuclear mixed valence copper(I/II) compound [CuI(CN)3CuII(tn)2] (1) (tn = propane-1,3-diamine) and its acetonitrile adduct [CuI(CN)3CuII(tn)2] · 2MeCN (2) have been synthesized. Complex 1 crystallizes triclinic, space group , a = 8.117(2) Å, b = 8.389(2) Å, c = 11.920(2) Å, α = 108.728(3)°, β = 100.024(3)°, γ = 104.888(4)°, Z = 2, and compound 2 monoclinic, space group P21/m, a = 8.752(2) Å, b = 13.243(3) Å, c = 9.549(2) Å, β = 114.678(4)°, Z = 2. In both crystal structures, the binuclear [CuI(CN)3CuII(tn)2] complex with slightly different bonding geometries is formed. One of the three nitrogen atoms of a CuI(CN)3 moiety is coordinated to Cu(II) at the apex of a square-pyramid with two chelating ligands tn on its base. The shortest intramolecular CuII?CuII distance in 1 is 5.640(7) Å. The EPR behaviour of 1 has been investigated at room temperature and at 77 K. The magnetic properties were measured in the temperature range 1.8-300 K. 相似文献
4.
Yuri V. Mironov Konstantin A. Brylev Sung-Jin Kim Svetlana G. Kozlova Vladimir E. Fedorov 《Inorganica chimica acta》2011,370(1):363-368
A hexarhenium cyanohydroxo anionic cluster complex [Re6Se8(CN)4(OH)2]4− was synthesized for the first time starting from [Re6Se8(OH)6]4−, which was crystallized as a salt of the composition Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) Å, c = 19.430(2) Å, V = 5938.3(10) Å3); compound 2 is crystallized in the monoclinic space group P21/n with two formula units per cell (a = 12.1845(13) Å, b = 8.6554(9) Å, c = 19.2568(19) Å, β = 91.081(2)°, V = 2030.5(4) Å3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) Å, b = 14.611(3) Å, c = 13.751(3) Å, V = 3981.2(13) Å3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4− was elucidated by DFT calculations. 相似文献
5.
Copper(II)-zinc(II) bimetallic imidazolate metal-organic framework compounds of composition CuaZnbIm2(a + b) (Im = C3H3N2), including Cu2ZnIm6 (1), were prepared in high yields from the metal oxides under mild aqueous conditions using a novel acid catalysis method. Mild acidic hydrothermal treatment of paramagnetic 1 (≥120 °C) gave diamagnetic Cu(I)-containing Cu2ZnIm4 (2) in high yield. The formation mechanism of 2 involves electron transfer from Im− to Cu(II), with concomitant formation of the unusual cyclotriimidazole, C9H6N6. Air-stable 2, characterized by single-crystal X-ray diffraction, crystallized in the tetragonal space group , with a = b = 10.9623(3), c = 6.3231(4) Å, α = β = γ = 90°, V = 759.86(6) Å3, and Z = 1. 相似文献
6.
Yi-Shan Song 《Inorganica chimica acta》2005,358(1):191-195
A novel chain-like luminescent samarium coordination polymer {Sm3(C8H4O4)4(C12N2H8)2(NO3)}n (C8H4O4 = phthalate, C12N2H8 = 1,10-phenanthroline) has been assembled by hydrothermal process. The title complex crystallizes in the monoclinic system, space group P2(1)/c, with lattice parameters a = 22.56(3) Å, b = 11.155(15) Å, c = 20.32(3) Å, β = 96.70(2)°, V = 5078(12) Å3, F(000) = 2964, GOF = 0.857, R1 = 0.0358, wR2 = 0.0597, Z = 4. Samarium ions exhibit different coordination modes from each other and lead to the unexpected high asymmetrical structure. To our knowledge, it is the first example of lanthanide coordination polymers comprising the three asymmetrical central Sm3+ fragments. The photophysical properties have been studied with excitation and emission spectra. 相似文献
7.
Nicolas Kerbellec Olivier Guillou Carole Daiguebonne Thierry Roisnel 《Inorganica chimica acta》2005,358(11):3246-3252
The reaction of Ln(III) ions with the precursor [Cu(opba)]2− in DMSO has afforded a series of isostructural compounds of general chemical formula Ln2[Cu(opba)]3(DMSO)6(H2O) · (H2O), where Ln(III) stands for a lanthanide ion and opba stands for ortho-phenylenebis(oxamato). The crystal structure has been solved for the Gd(III) containing compound. It crystallizes in the orthorhombic system, space group Pbn21 (No. 33) with a = 9.4183(2) Å, b = 21.2326(4) Å, c = 37.9387(8) Å and Z = 4. The structure consists of ladder-like molecular motifs parallel to each other. To the best of our knowledge, this is the first Ln(III)Cu(II) coordination polymer family exhibiting the same crystal structure over the whole lanthanide series. The magnetic properties of the compounds have been investigated and the magnetic behavior of the Gd(III) containing compound was studied in more detail. 相似文献
8.
Chihiro Kachi-TerajimaHitoshi Miyasaka Tomohiko IshiiKen-ichi Sugiura Masahiro Yamashita 《Inorganica chimica acta》2002,332(1):210-215
The ligand substitution reaction of Ru2(O2CCH3)4Cl with 2-amino-4,6-dimethylpyrimidine (Hadmpym) under gentle refluxing conditions in methanol led to the formation of a bridging-ligand mono-substituted compound, [Ru2(O2CCH3)3(admpym)(Cl)(MeOH)] (1). Compound 1 crystallized in monoclinic space group P21/n (no. 14) with a=8.3074(8) Å, b=12.3722(8) Å, c=18.913(1) Å, β=95.559(3)°, V=1934.8(3) Å3, and Z=4. Temperature dependence of the magnetic susceptibility of 1 revealed it to be in a spin ground state S=3/2 arising from the electronic configuration of σ2π4δ2(δ*π*)3. Compound 1 undergoes three metal-centered redox reactions in electrochemistry: E1/2 (ox)=+0.72 V (Ia/Ic<1, ΔEp=0.17 V); E1/2 (1,red)=−0.65 V (Ia/Ic≈1, ΔEp=0.10 V); and E1/2 (2,red)=−1.80 V (Ia/Ic?1, ΔEp=0.16 V). Then, the redox species produced by electrolysis were characterized by spectroscopic studies. 相似文献
9.
Jens Müller Fabian-Alexander Polonius Michael Roitzsch 《Inorganica chimica acta》2005,358(4):1225-1230
Reaction of 9-methyl-1-deazapurine (9-MeDP) with Hg(CF3COO)2 in the presence of NaNO3 yields the title compound [Hg(9-MeDP)2](NO3)2 · H2O with the two 9-MeDP ligands bound to the metal ion via their N7 positions. The X-ray structure is reported: monoclinic, P21/c (no. 14), a = 5.4015(11), b = 20.467(4), c = 17.775(4) Å, β = 97.00(3)°, V = 1950.4(7) Å3, Z = 4. Hg is eight-coordinate with two trans-oriented Hg-N bonds (2.073(3) and 2.075(3) Å) and three nearly coplanar, bidentate nitrate moieties (Hg-O: 2.716(3)-2.985(4) Å), leading to a distorted hexagonal bipyramidal environment of the metal ion. Within this structure, the nitrate ions form a honeycomb-like chain structure with HgII being positioned inside the combs. This work represents the first report of such geometry for a transition metal ion surrounded by symmetrically bidentate nitrate ions. The corresponding nucleoside, 1-deazapurine 2′-deoxyribonucleoside, also forms a stable 2:1 complex with HgII, as was shown by 1H NMR spectroscopy, making it a potential candidate for incorporation into nucleic acids based on metal-mediated base pairs. 相似文献
10.
Reaction of [Ru2(O2CMe)4]Cl with K3[Cr(CN)5NO] in water forms Hx[RuII/III2(O2CMe)4]3−x-[Cr(CN)5NO]·zH2O (x = 0.2) that magnetically orders at 4.0 K and possesses an interpenetrating body centered cubic [a = 13.2509(2) Å] structure with random locations of the bridging nitrosyl ligands, and x/3 vacant cation sites. Similarly, the aqueous reaction of [Ru2(O2CMe)4]Cl with Na2[Fe(CN)5NO] forms paramagnetic [Ru2(O2CMe)4]2[Fe(CN)5NO]·H2O, which has a similar tetragonal interpenetrating structure [a = 13.0186(1) Å, c = 13.0699(2) Å] where the NO ligands are presumably nonbridging and 1/3 of the expected cation sites are unoccupied. The presence of uncoordinated NO sites in addition to missing neighboring [Ru2(O2CMe)4]+ units, results in significant vacancies (or holes) in the lattice. 相似文献
11.
A 1,4-disubstituted dibenzofuran derivative of 1,4,7,10-tetraazacyclododecane (cyclen), L1, has been prepared by the direct reaction of cyclen and chloroacetyldibenzofuran and the mono-substituted derivative, L2, by reaction of chloroacetyldibenzofuran and 1,4,7-tris(t-butoxycarbonyl)-1,4,7,10-tetraazacyclododecane followed by deprotection with trifluoroacetic acid. The ligands were characterized by 1H and 13C NMR spectroscopy, IR spectroscopy and mass spectrometry. The reaction of the 1,4-disubstituted dibenzofuran cyclen, L1, with Cu(ClO4)2·6H2O in methanol yielded crystals of [CuL1](ClO4)2·MeOH·1/2H2O that were suitable for single crystal structural analysis. The X-ray structure confirmed that the 1,4-disubstituted dibenzofuran cyclen had been formed. The copper(II) coordination sphere in the complex cation, [CuL1]2+, is occupied by four nitrogen atoms from the macrocycle and an amide oxygen donor from one dibenzofuran pendant group. As is typical for copper(II)-cyclen complexes, the Cu(II) centre sits above the plane of the macrocycle nitrogen towards the oxygen donor, in this case by 0.5 Å. Fluorescence emission studies indicate that coordination of the macrocycle to either copper(II) or zinc(II) results in a decrease in emission with respect to the emission of the pure ligand. 相似文献
12.
Knoevenagel condensation of 4-(dimethylamino)benzaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) gives the donor-acceptor ligand 2-(4-dimethylaminobenzylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (dbpcd). The reaction of dbpcd with PtCl2(cod) affords the platinum(II) complex PtCl2(dbpcd) in high yield. The free dbpcd ligand and PtCl2(dbpcd) have been isolated and fully characterized in solution by IR and NMR spectroscopies, and the solid-state structure of PtCl2(dbpcd) determined by X-ray diffraction analysis. PtCl2(dbpcd), as the 1.5CH2Cl2 solvate, crystallizes in the triclinic space group , a = 11.7412(7) Å, b = 12.0486(7) Å, c = 14.4781(9) Å, α = 82.866(1), β = 75.049(1), γ = 83.905(1), V = 1957.6(2) Å3, Z = 2, and Dcalc = 1.678 mg/m3, R = 0.0291 and wR2 = 0.0723 for 8315 reflections with I > 2σ(I). The molecular structure of PtCl2(dbpcd)·1.5CH2Cl2 consists of a square-planar platinum architecture containing two chlorines and the ancillary dbpcd diphosphine ligand. The redox properties of the dbpcd ligand and PtCl2(dbpcd) have been explored by cyclic voltammetry, and these data are discussed with respect to extended Hückel MO calculations. 相似文献
13.
A series of tridentate ligands consisting of mixed aromatic and aliphatic amine derivatives of single amino acid chelates and phenylpiperazine have been developed, and their reactions with [NEt4]2[ReBr3(CO)3] have been investigated. The compounds [Re(CO)3{(NC5H4CH2)NCH3(C2H4)NHCH3}]Br (4), [Re(CO)3{(NC5H4CH2)NCH3(C2H4)NCH3(CH2)xCOOC2H5}]Br (x = 1, 5; x = 4, 6) [Re(CO)3{(NC5H4CH2)NH(C2H4)N(CH3)2}]Br (7), [Re(CO)3{(NC5H4CH2)N(CH 2COOC2H5)(C2H4)N(CH3)2}]Br (8) and [Re(CO)3(NC5H4CH2)(C2H4NH2)N(CH2)3-CH3Ophenpip]Br (9) (phenpip: phenylpiperazine, -C6H4-(CH2CH2)2N-) were prepared and characterized by elemental analysis, NMR, IR, HSMS and X-ray crystallography. All complexes exhibit fac-{Re(CO)3N3} coordination geometry in the cationic molecular unit. Crystal data for C13H17BrN3O3Re (4): orthorhombic, Pbca, a = 13.4510(8) Å, b = 10.5728(6) Å, c = 22.5378(13) Å, V = 3205.2(3) Å3, Z = 8; C17H23BrN3O5Re (5): orthorhombic, Pcca, a = 16.5907(7) Å,b = 14.8387(6) Å, c = 16.7075(7) Å, V = 4113.1(3) Å3, Z = 8; C13H25BrN3O7Re (7 · 4H2O): monoclinic, P21/n, a = 14.0698(17) Å, b = 9.6760(12) Å, c = 15.6099 (19) Å, β = 114.930(2)°, V = 1927.1(4) Å3, Z = 4; C17H23BrN3O5Re (8): monoclinic, P21/n, a = 7.5312(5) Å, b = 16.0366(10) Å, c = 16.8741(10) Å, β = 98.9990(10)°, V = 2012.9(2) Å3, Z = 4. 相似文献
14.
A novel three-dimensional organically templated zincophosphite, [C6N2H18] · [Zn3(HPO3)4], was synthesized under milder hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, differential thermal-thermogravimetric analysis, powder X-ray diffraction, 31P MAS NMR spectrum, and IR spectroscopy. It crystallizes in the monoclinic system, space group C2/c with cell parameters: a = 8.7820(4) Å, b = 14.9417(7) Å, c = 15.4943(5) Å, β = 92.940(2)°, and Z = 4. The structure consists of a network of strictly alternating ZnO4 tetrahedra and pseudo-pyramid, forming 4-membered ring chains. The structure has a 4.8.16-net and 8- and 16-membered ring channels where completely protonated N,N,N′,N′-tetramethylenediamine cations are encapsulated. The structure is stabilized by template-to-framework hydrogen bonding. In phosphites system, this compound possesses extra-large-pores. 相似文献
15.
A novel fluorinated iron phosphite Fe2(HPO3)F2 (1) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pnma (No. 51) with a = 7.3458(15) Å, b = 10.038(2) Å, c = 5.4947(11) Å, V = 405.16(14) Å3, Z = 4. Its structure is built up from iron(II) oxygen-fluorine FeO3F3 octahedra and HPO3 pseudo-tetrahedra, giving rise to a 3D inorganic framework. The infinite -Fe-O-Fe-F-Fe- linkage and -Fe-F-Fe- layer in the framework are the noteworthy structural features. Mössbauer spectrum shows the presence of Fe2+ in the octahedral coordination. Magnetic measurements indicate the existence of antiferromagnetic interactions. 相似文献
16.
Anna M.M. Meij 《Inorganica chimica acta》2005,358(4):1005-1011
The aqueous solution behaviour of the equilibrium related cis-[PdCl2(PTA)2] and [PdCl(PTA)3]Cl complexes has been investigated in the presence of acid and iodide ions. Several of the resulting species were identified and a reaction scheme accounting for identified complexes is proposed. The crystal structures of trans-[PdI2(PTA-H)2][PdI3(PTA)]2 · 2H2O (1) (PTA-H+ = protonated form of PTA) and trans-[PdI2(PTA)2] (2) are reported. The geometry around the Pd(II) metal centre in 1 (for both the cation and anion) and 2 is distorted square planar. The PTA ligands occupy a trans orientation in the cation of 1 and in complex 2. Compound 1 represents a rare example of a Pd(II) system wherein the cation:anion pair, in a 1:2 ratio, are both coordination complexes. It is the first d8 Ni-triad square planar complex containing only one PTA ligand and only the second platinum group metal complex. For the cation in 1, the bond distances and angles are Pd(1)-P(1) = 2.2864(16) Å, Pd(1)-I(1) = 2.6216(7) Å, P(1)-Pd(1)-P(1)′ = 180.00(7)° and P(1)-Pd(1)-I(1) = 87.62(4)°, while in the anion the bond distances are Pd(2)-P(2) = 2.2377(15) Å, Pd(2)-I(4) = 2.5961(13) Å, Pd(2)-I(2) = 2.6328(13) Å, Pd(2)-I(3) = 2.6513(8) Å, while the angles are P(2)-Pd(2)-I(4) = 90.00(5)°, P(2)-Pd(2)-I(2) = 89.69(5)°, I(4)-Pd(2)-I(2) = 179.57(2)°, P(2)-Pd(2)-I(3) = 175.19(4)°, I(4)-Pd(2)-I(3) = 90.29(4)° and I(2)-Pd(2)-I(3) = 90.05(4)°. Bond distances and angles of the coordination polyhedron in 2 are Pd-P = 2.327(3) Å, Pd-I = 2.5916(10) Å, P-Pd-I = 89.13(7)° and P-Pd-P = 180.00(13)°. The average effective- and Tolman cone angles for the two ligands, calculated from the crystallographic data, are 115° and 117° for PTA and PTA-H, respectively. 相似文献
17.
The synthesis and structure of a new 1-D molybdenum-arsenic compound based on the bi-capped Keggin anion [MoVI6MoV6O36(AsO4)(MoVO)2]− have been reported, and its catalytic property has been examined. The title compound was characterized by IR, TG and X-ray diffraction analysis. Single crystal X-ray diffraction shows that it crystallizes in cubic crystal system, space group Pn-3m with cell dimension: a = 11.749(2) Å, V = 1622.0(5) Å3, Z = 2. Its structure has a 1-D infinite chain, in which the bi-capped Keggin anions are connected by sharing one terminal oxygen atom from the caps. The compound shows a moderate styrene conversion (48%), the major product for the oxidation of styrene is benzaldehyde (85.2%). 相似文献
18.
Antonis Vlachos Catherine P Raptopoulou Yiannis Sanakis Georgios Diamantopoulos Marina Karayanni Aris Terzis 《Inorganica chimica acta》2004,357(11):3162-3172
Complex [Cr3O(O2CPh)6(MeOH)3](NO3) · 2MeOH (1 · 2MeOH) has been synthesized from the one-pot reaction between Cr(NO3)3 · 9H2O and NaO2CPh in MeOH. The structure of the complex has been solved by single-crystal X-ray crystallography. It crystallizes in the monoclinic space group P21/n with a=14.716(6) Å, b=22.569(8) Å, c=15.755(6) Å, β=95.02(1)°, V=5212.5(4) Å3 and Z=4. Although the cation does not possess any crystallographically imposed symmetry element, its {Cr3(μ3-O)} core is nearly symmetric. Each CrIII…CrIII vector is further bridged by two η1:η1:μ2 benzoates, with a terminal MeOH molecule completing octahedral coordination at each metal ion. The crystal structure consists of layers that are parallel to (0 1 0) crystallographic plane and are formed through π-π stacking interactions and hydrogen bonds. Variable-temperature magnetic susceptibility and solid-state 1H NMR studies indicate that the total spin value of the ground state is 1/2. EPR experiments reveal the existence of a distribution of trimers with axial anisotropy in the g tensor. 相似文献
19.
Two polymorphic crystal structures of the title compound, dibromo[(−)-sparteine-N,N′]copper(II), 1, were determined. The structures of two isomorphs of 1, 1a [orthorhombic, P212121, a=11.0463(9) Å, b=11.9839(15) Å and c=12.7835(19) Å] and 1b [orthorhombic, P212121, a=7.6779(9) Å, b=12.0927(14) Å and c=18.090(2) Å], are composed of the same basic structural unit, Cu(C15H26N2)Br2. The bond distances in the molecular structures of 1a and 1b are identical to each other within the esds. However, there are slight differences in the bond angles around the Cu(II) center and considerable differences in their packing structure. Crystal 1a exhibits weak anti-ferromagnetism (J=−1.89 cm−1) as opposed to the magnetically isolated paramagnetism observed for the analogous dichloro[(−)-sparteine]copper(II), 2. The results of a magneto-structural investigation of 1a and 2, and other supporting evidence, suggest that the pathway for the weak antiferromagnetic super-exchange in 1a might be through a Cu-Br ? Br-Cu contact. 相似文献
20.
Eric Burkholder 《Inorganica chimica acta》2006,359(1):261-266
The hydrothermal reaction of CuBr2 and tpyprz in the presence of NH4VO3 and HF for 72 h at 170 °C provided [(tpyprz)3Cu10Br10] (1) in 20% yield. The two-dimensional structure of 1 may be described as Cu(I)-tpyprz chains, linked through {Cu4Br5}− clusters in the ac-plane and decorated with {Cu3Br5}2− clusters projecting from one face of the layer in the b-direction. The Cu(I) sites exhibit distorted trigonal coordination {CuBr3} and distorted tetrahedral geometries, {CuBr2N2} and {CuN4}. Crystal data for 1: monoclinic space group C2, a = 12.7561(8) Å, b = 19.359(1) Å, c = 15.860(1) Å, β = 97.178(1)°, V = 3885.8(4) Å3, Z = 2, Dcalc = 2.222 g cm−3, μ(Mo Kα) = 78.75 cm−1. 相似文献